JPH0491122A - Reactive unsaturated monomer composition containing carboxyl group and production thereof - Google Patents

Abstract

PURPOSE:To obtain the title composition capable of simultaneously providing excellent flexibility and adhesion and providing hydrophilic property, etc., in addition to improvement of some characteristics as a coating base. CONSTITUTION:The aimed composition containing a compound having a structure expressed by formula II (R<1> is H or 1-10C alkyl; R<2> and R<3> are H or 1-5C alkyl and R<2> and R<3> can be simultaneously replaced by each group; R is divalent organic compound residue; x is 0 or 1-10; y is 2-10; z is 3-7; n is 1-20) and containing a carboxyl group and obtained by reacting (A) a compound expressed by formula I with (B) an acid anhydride. Furthermore, a compound obtained by subjecting a lactone compound to ring-opening addition polymerization with unsaturated compound having OH group is preferably used as the component A and a dibasic acid anhydride expressed by formula III is preferably used as the component B.

Description

Detailed Description of the Invention (Industrial Application Field) The present invention relates to a reactive composition containing a carboxyl group whose main component is a reaction product of a lactone polymer having an unsaturated group and an acid anhydride or a dicarboxylic acid. It relates to products and their manufacturing methods.

(Prior Art) Conventionally, carboxylic acids having vinyl groups have been copolymerized with various vinyl monomers, and the resulting polymers have been used as thermosetting paints,
Used in a wide range of applications such as adhesives, fuborimer modifiers for paper processing, crosslinking agents, fiber treatment agents, anionic electrodeposition paints, etc., or as intermediates, molding plastics, synthetic rubbers, water-absorbing polymers, etc. It is being

Furthermore, in recent years, flexibility and weather resistance have been particularly required, and a method of adding a lactone compound to a carboxylic acid having an unsaturated group has been proposed (Japanese Patent Application Laid-open No. 67446/1983).

This unsaturated group-containing carboxylic acid can be radical copolymerized with a fluorinated ethylene monomer such as chlorotrifluoroethylene, along with alkyl vinyl ether, fatty acid vinyl ester, alkyl allyl ether, etc.
It can be used as a fluorine-based paint resin having a carboxyl group.

However, although this method does yield a compound that can impart flexibility, a large amount of unreacted carboxylic acid with unsaturated groups remains, and a step is required to separate it.
In addition, a relatively large amount of strong acid catalysts such as sulfuric acid and p-1 luenesulfonic acid are used, and the process for removing them must also be considered.

Furthermore, this method has problems such as coloring of the reaction product.

Furthermore, alcohols having vinyl groups can also be used as fluorocoating resins such as chlorotrifluoroethylene together with various unsaturated monomers.

According to the method of adding a lactone polymer to alcohol having a vinyl group (Japanese Unexamined Patent Publication No. 64-16815), a compound capable of imparting flexibility and a good hue can be obtained, but it is difficult to improve adhesion. It has not yet been reached.

Furthermore, as mentioned above, a hydroxyl group-containing copolymer is added to a tribasic acid anhydride represented by -bottom O [where R represents a divalent organic group] in an organic solvent. A method of converting at least a part of the hydroxyl group into an ester group represented by the general formula -0-C-R-COOH [wherein R represents a divalent organic compound residue] (Japanese Patent Application Laid-Open No. 63-54469)
According to the method, adhesion is improved, but this reaction requires a relatively large amount of catalyst, and this catalyst reduces weather resistance.

(Problems to be Solved by the Invention) In order to solve these problems, the present inventors conducted intensive studies in order to obtain a compound that can provide excellent flexibility and adhesion. The present inventors have discovered that a compound synthesized by ring-opening addition polymerization of a lactone compound to an alcohol having the formula and further reacting with a tribasic acid anhydride is extremely effective, and has completed the present invention.

(Structure of the Invention) That is, the present invention provides the following, "The following - Bottom (1) % formula %" [However, in the above - Bottom (1), R1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, R, R is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and RR can be replaced with each group at the same time.R is a 2-carbon residue of an organic compound.X is 0 and 1-10 can take any integer from 2 to 10. Z can take any integer from 3 to 7. n can take any integer from 1 to 20. A carboxyl group-containing reactive unsaturated monomer composition containing a compound having a structure represented by the following general formula (Nl) R1 10 C-→C→-〇 ←-H 2n R3 ... (Ill) The following general formula (1) is characterized by reacting an acid anhydride with a compound having the structure In (1) and (Ill), R1 is a hydrogen atom or a C7 alkyl group having 1 to 10 carbon atoms. RR is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R and R3 are at the same time each R is a divalent organic compound residue. X can be 0 and any integer from 1 to 10. y is 2
Can take any integer up to ~10 2 is 3~
It can be any integer up to 7. n is 1 to 20
A method for producing a carboxyl group-containing reactive unsaturated monomer composition comprising a compound having the structure shown in the following.

The present invention further provides a compound obtained by ring-opening addition polymerization of a lactone compound with an unsaturated compound having a hydroxyl group, which is represented by the general formula (in which R represents a divalent organic group). Its feature is that the terminal can be converted from a hydroxyl group to a carboxyl group by the action of a tribasic acid anhydride.

A carboxylic acid type reactive unsaturated monomer composition obtained by reacting 1 mole of this tribasic acid anhydride, that is, a reactive composition containing a compound having the structure of general formula (I). It is.

In the compound having the structure of general formula (I), R1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms, and varies depending on the unsaturated compound having a hydroxyl group used as a raw material.

R2 and R3 are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms depending on the lactone monomer used as a raw material, and R and R3 can be changed to each group at the same time.

R is the residue of a tribasic acid anhydride.

For example, when phthalic anhydride is used as the tribasic acid anhydride described below, R becomes a benzene nucleus having a bond at the meta position.

X can be 0 or any integer from 1 to 10.

y can take any integer from 2 to 10. For example, as an alcohol having an unsaturated group described below, 2
When -hydroxyethyl allyl ether is used, R1 is necessarily hydrogen, X is 1, and y is 3.

Z is a numerical value that varies depending on the lactone compound used, and can be any integer from 3 to 7.

For example, when ε-caprolactone is used as the lactone compound described below, R2R3 will inevitably become hydrogen,
2 becomes 5.

n corresponds to the degree of polymerization of the lactone moiety, and is preferably a value of 1 to 20, which can be arbitrarily controlled by the molar ratio of the lactone compound and the unsaturated compound having a hydroxyl group.

The lactone polymer having an unsaturated group represented by the general formula (11) used in the present invention can be obtained by carrying out a ring-opening addition reaction of a lactone to an alcohol having an unsaturated group in the presence of a catalyst.

Examples of the alcohol having an unsaturated group, which is a raw material for producing the lactone polymer having an unsaturated group represented by the general formula (11), include 2-hydroxyethyl (meth)allyl ether, 3-hydroxypropyl (meth) Allyl ether, 2-hydroquinepropyl (meth)allyl ether, 4-hydroxybutyl (meth)allyl ether, 3
-Hydroquine butyl (meth)allyl ether, 2-hydroxy-2-methylpropyl (meth)allyl ether,
5-hydroxypentyl (meth)allyl ether, 6-hydroxyethyl (meth)allyl ether, 2-hydroxyethyl vinyl ether, 3-hydroxypropyl vinyl ether, 2-hydroquine propyl vinyl ether, 4
-hydroquine butyl vinyl ether, 3-hydroquine butyl vinyl ether, 2-hydroquine-2-methylpropyl vinyl ether, 5-hydroquine pentyl vinyl ether, 6-hydroxyethyl vinyl ether, and the like.

The other raw material lactones include ε-cabrolactone, 3,3.5-trimethylcaprolactone, 3
, 5.5-trimethylcaprolactone, β-methyl-δ
- Examples include valerolactone.

In addition, as a catalyst, organic titanium compounds such as tetrabutyl titanate, tetrapropyl titanate, tetraethyl titanate, tin octylate, nbutyl tin oxide,
Examples include organic tin compounds such as dibutyltin laurate and dibutyltin ophtate, and tin halides such as stannous chloride, stannous bromide, and stannous iodide.

This reaction is carried out at 70-220°C, preferably 100-180°C.
Perform at ℃.

At temperatures lower than 70°C, the reaction rate is low, and 220°C
Temperatures higher than 0.degree. C. are undesirable because the lactone compound decomposes.

Further, as the tribasic acid anhydride to be reacted with the lactone polymer having an unsaturated group represented by the general formula (11),
Examples include succinic anhydride, flutaric anhydride, phthalic anhydride, hexahydrophthalic anhydride, 3-methylhexahydrophthalic anhydride, 4-methylhexamethylphthalic anhydride, and the like.

This reaction is carried out at 70-150°C, preferably 80-1,20°C.
Perform at ℃.

At temperatures lower than 70°C, the reaction rate is low;
At temperatures above ℃, the degree of coloration of the reactants increases, and further, compounds with unsaturated groups at both ends due to decomposition reactions and condensation reactions between the generated carboxyl groups and unreacted hydroxyl groups as shown in formula (v) below. This is not desirable because it generates

When a target product containing this by-product is copolymerized with other vinyl monomers, three-dimensional crosslinking occurs in the resin, resulting in a significant increase in viscosity or even gelation.

CH2-CH-R-0-Co-R OOH + CH2-CH-R"OH ↓ CH2-CH-R--0-CO-R- COO-R0H-CH-CH2 + H2O...(v) [In the formula, R and R-R'' represent a divalent organic group which is a residue of a divalent organic compound].

This reaction proceeds without a catalyst, but may be carried out in the presence of a suitable catalyst.

As catalysts, metal carboxylates such as sodium acetate, potassium acetate, lead acetate, lead stearate, etc., alkali hydroxides such as sodium hydroxide, potassium hydroxide, etc., alkali metal carbonates such as sodium carbonate, potassium carbonate, etc. , alkali metal alcoholades such as sodium methylate, sodium ethylate, potassium methylate, potassium ethylate etc., quaternary ammonium salts such as triethylbenzylammonium, triethylbenzylammonium, tetraethylammonium, tetramethylammonium etc., amines such as pyridine, Basic catalysts such as triethylenediamine and triethylamine are preferred.

The carboxyl group introduction reaction is also promoted by acid catalysts such as sulfuric acid and para-toluenesulfonic acid, but in this case, depending on the reaction conditions, a condensation reaction between the generated carboxyl group and unreacted hydroxyl group as shown in reaction formula (■) may occur. This is not preferable because it also accelerates reaction conditions and requires careful setting of reaction conditions.

The amount of catalyst used is lO~5000ppm based on the starting material.
, preferably 10 to 11000 pp.

If the amount used is less than 10 ppm, the reaction will be slow, and on the contrary, the reaction will be slower than 50 ppm.
If it exceeds 0.00 ppm, the reaction rate will increase or side reactions will occur, resulting in coloring of the product, which is not preferable.

The reaction may be carried out without a solvent or in an inert solvent such as toluene or xylene.

The reason for using an inert solvent is to have the effect of lowering the viscosity of the reaction crude liquid in the system after the reaction is completed, and to facilitate temperature control during the reaction.

Whether or not an inert solvent is used can be arbitrarily selected depending on the intended use of the carboxyl group-containing reactive unsaturated monomer composition of the present invention.

That is, it can be used for products such as paints that may contain solvents.

Further, the inert solvent may be added to the reaction crude solution after the reaction is completed.

The amount of inert solvent used is 5 to 80% by weight, preferably 1
It is 0 to 50% by weight.

The carboxyl group-containing reactive unsaturated monomer composition of the present invention is extremely effective as a reactive monomer that can simultaneously impart excellent flexibility and adhesion, and can be used as a paint base as described above. In addition to improving the properties of
It can also be applied to the introduction of crosslinking sites and ion exchange groups.

Hereinafter, specific examples of the present invention will be explained with reference to Examples, but the present invention is not limited to these Examples.

Synthesis Example 1 2,500 g of 2-hydroxyethyl allyl ether was placed in a flask equipped with a thermometer, nitrogen inlet tube, cooling tube, and stirrer.
ε-caprolactone 2792.4 g and ε-caprolactone solution (1%) of stannous chloride as catalyst 2.68
After reacting at a reaction temperature of 170° C. for 11 hours while blowing nitrogen, the mixture was cooled to room temperature and its general properties were measured, and the results were as follows.

Hue (APHA) 40 Viscosity (c p
/ 45℃) 10 Moisture (%) 0.05 Acid value (m
gKOH/g) 1, 25
Hydroxy value (mgKOH/g) 258.3 Further, residual ε-caprolactone was analyzed by gas chromatography and found to be 0.38% by weight. This is raw material A
shall be.

Synthesis Example 2 306.4 g of 2-hydroxyethyl allyl ether was placed in a flask equipped with the same equipment as in Synthesis Example 1.

1711.1 g of ε-caprolactone and 1.2 g of 1% stannous chloride/ε-caprolactone solution as a catalyst were charged, and after reacting at a reaction temperature of 170°C for 8 hours while blowing nitrogen, the mixture was cooled to room temperature and the general properties were determined. The results were as follows.

Hue (APHA) 60 Viscosity (cp/
45℃) 90 Moisture (%)
0.05 acid value (mgKOH/g) 0
．． 88 Hydroxy value (mgKOH/g) 80.5 Residual ε-caprolactone was analyzed by gas chromatography and found to be 0.454% by weight. This is called raw material B.

Example 1 Raw V4A6 was added to a flask equipped with the same equipment as in Synthesis Example 1.
71.0 g of hexahydrophthalic anhydride and 473.5 g of hexahydrophthalic anhydride were charged and reacted at a reaction temperature of 80° C. for 8 hours while blowing nitrogen, and then cooled to room temperature. General properties were measured and found as follows.

Hue (APHA) 60 Viscosity (cp/
45℃) 167AV (mgKOH/g)
152 Moisture (%) 0
．． 03GPC showed a pattern as shown in Figure 1.

This is a mixture of compounds having different numbers of added moles of ε-caprolactone.

The H-NMR spectrum was obtained using JNM-E from JEOL Ltd.
It was obtained by determining M1 in CDCl1 at room temperature using an X90 spectrometer, and in the spectrum (Figure 2),
The hydrogen of the double bond of the allyl group has a multiplet δ5,1~5.4 and 65.7~6°2 (H'), the methylene hydrogen adjacent to the oxygen has a multiplet NjA63.5-3.8 (Hc), 6
4.0-4.5 (HbSH' and Hl), methylene hydrogen multiplet 62.7-3.0 (H'), other methylene hydrogen δ1,2-2.5 (H' Hh), carboxylic acid Protons have a broad signal δ1(J, 1 (H
) can be attributed to each.

The IR spectrum was determined using Shimabara Seisakusho's IR-435.
It was applied to an aCl plate and measured.

In the spectrum (Fig. 3), the broad absorption near 3000 cm-' is due to the carboxyl group, and the 1717c
Carbonyl absorption at m-', 3071 cm-' 16
Absorption due to double bonds was observed at 44 cm-' and 918 cm-'.

From the above results, this product has the following g8 structural formula [however,
It is clear that in the above structural formula, R3 is represented as follows.

Example 2 Raw material A324 was placed in a flask equipped with the same equipment as in Synthesis Example 1.
．． 4 g, hexahydrophthalic anhydride, 228.9 g, as a catalyst, benzyltriethylammonium bromide 0.5
After charging 5 g and reacting at a reaction temperature of 80° C. for 8 hours while blowing nitrogen, the mixture was cooled to room temperature, and the general properties were measured as follows.

Hue (APHA) 140 Viscosity (cp/
45℃) 175AV (mgKOH/g)
150 moisture (%)
0.05 Example 3 Raw material 8134 was placed in a flask equipped with the same equipment as Synthesis Example 1.
After charging 5.7 g of hexahydrophthalic anhydride and 305.3 g of hexahydrophthalic anhydride and reacting at a reaction temperature of 80° C. for 7 hours while blowing nitrogen, the mixture was cooled to room temperature, and the general properties were measured as follows.

Hue (APHA) 50 Viscosity (cp/
45℃) 240 AV (mg KOH/g)
68 Moisture (%) 0.0
2 Example 4 Raw material A86.
After charging 53 g of succinic anhydride and 40.03 g of succinic anhydride and reacting for 10 hours at a reaction temperature of 120''C while blowing nitrogen, the mixture was cooled to room temperature, and the general properties were measured as follows.

Hue (APHA) 80 Acid value (mgKO
H/g) 189 Moisture (%)
0.08 Example 5 Raw material A365 was placed in a flask equipped with the same equipment as in Synthesis Example 1.
゜1g, 396.3g of succinic anhydride, and 126g of tetraethylammonium bromide as a catalyst, and after reacting for 10 hours at a reaction temperature of 120°C without blowing nitrogen,
After cooling to room temperature, the general properties were measured as follows.

Hue (APHA) 160 Acid value (mgK
OH/g) 162 Moisture (%)
0.12 Example 6 Raw material 8134 was placed in a flask equipped with the same equipment as in Synthesis Example 1.
4.6 g of succinic anhydride and 198.1 g of succinic anhydride were charged, and after reacting at a reaction temperature of 120° C. for 10 hours while blowing nitrogen, the mixture was cooled to room temperature, and the general properties were measured as follows.

Hue (APHA) 80 Acid value (mgK
OH/g) 75 Moisture (%)
0.06

[Brief explanation of the drawing]

FIG. 1 is a GPC chart of a compound obtained by reacting the compound obtained in Synthesis Example 1 (raw material A) with hexahydrophthalic anhydride. FIG. 2 is the same 'H-NMR spectrum chart, and FIG. 3 is the same infrared absorption spectrum chart.

Claims (1)

[Claims] (1) The following general formula (I) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(I) [However, in the above general formula (I), R^1 is a hydrogen atom or It is an alkyl group having 1 to 10 carbon atoms. R^2
, R^3 is a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R^2 and R^3 can be replaced with each group at the same time. R is a divalent organic compound residue. x can be 0 or any integer from 1 to 10. y
can take any integer from 2 to 10. z can take any integer from 3 to 7. n can take any integer from 1 to 20.] A reactive unsaturated monomer composition containing a carboxyl group, including a compound having the structure shown below. (2) The compound represented by the general formula (I) has mathematical formulas, chemical formulas, tables, etc.▼... (II) [However, in the above general formula (II), R is a divalent organic compound residue. It is. n can take any integer from 1 to 20] The carboxyl group-containing reactive unsaturated monomer composition according to claim (1). (3) The following general formula (I
II) ▲There are mathematical formulas, chemical formulas, tables, etc.▼...The following general formula (I), which is characterized by reacting a compound having the structure shown in (III) with an acid anhydride ▲Mathematical formulas, chemical formulas, tables, etc. Yes▼▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(I) [However, in the above general formulas (I) and (III),
R^1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R^2 and R^3 are a hydrogen atom or an alkyl group having 1 to 5 carbon atoms, and R^2 and R^3 can be replaced with each group at the same time. R is a divalent organic compound residue. x can be 0 or any integer from 1 to 10. y can take any integer from 2 to 10. z
can take any integer from 3 to 7. n is 1
can be any integer from 20 to 20.] A method for producing a carboxyl group-containing reactive unsaturated monomer composition comprising a compound having the structure shown below. (4) The following general formula (IV) ▲There are mathematical formulas, chemical formulas, tables, etc.▼... (IV) The following general formula (I ) ▲There are mathematical formulas, chemical formulas, tables, etc.▼・・・(I) [However, in the above general formulas (I) and (IV),
R^1 is a hydrogen atom or an alkyl group having 1 to 10 carbon atoms. R^2, R^3 are hydrogen atoms or carbon atoms 1 to 5
is an alkyl group, and R^2 and R^3 can be replaced with each group at the same time. x can be 0 or any integer from 1 to 10. y can take any integer from 2 to 10. z can be any integer from 3 to 7. n can take any integer from 1 to 20.] A method for producing a carboxyl group-containing reactive unsaturated monomer composition containing a compound having the structure shown below.